Wet film-forming substance

Abstract

To provide a polyurethane resin composition excellent in wet film-forming property by using a biomass raw material.SOLUTION: A wet film-forming material of a polyurethane resin composition containing a polyurethane resin (X) having polyol (A) and polyisocyanate (B) as the raw materials, and an organic solvent (Y) is such that: the polyol (A) contains polycarbonate polyol (A-1) having biomass-derived decanediol as the raw material; and the polyisocyanate (B) contains aromatic polyisocyanate. It is preferable that the polycarbonate polyol (A-1) further has butanediol as the raw material, and the polyol (A) further contains polyether polyol (A-2).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a wet film formed from a polyurethane resin composition.

Background Art

[0002] Polyurethane resin has characteristics of being flexible and tough, and has excellent texture, so it is widely used in the production of artificial leather, synthetic leather, etc. In particular, when used in artificial leather or synthetic leather, an intermediate layer made of urethane resin is often formed to impart texture and a sense of volume.

[0003] The urethane resin used for the intermediate layer generally takes the form of a resin solution with N,N-dimethylformamide, which has excellent solubility in the urethane resin. By applying this urethane resin solution to a substrate and immersing it in water, a porous intermediate layer is formed by the substitution action between the resin solution and water (see, for example, Patent Document 1).

[0004] On the other hand, against the backdrop of problems such as global warming and depletion of petroleum resources, the global demand for environmentally friendly materials using biomass raw materials such as plants is increasing. The use of biomass raw materials can contribute to the formation of a sustainable society in that it can reduce the consumption of fossil resources such as petroleum. However, at present, wet films using biomass raw materials have not yet been developed.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] The problem to be solved by the present invention is to provide a wet film-forming product of a polyurethane resin composition that uses biomass raw materials and has excellent wet film-forming properties.

Means for Solving the Problem

[0007] The present invention provides a wet film-forming product of a polyurethane resin composition containing a polyurethane resin (X) and an organic solvent (Y) using a polyol (A) and a polyisocyanate (B) as raw materials, wherein the polyol (A) contains a polycarbonate polyol (A-1) using a biomass-derived decanediol as a raw material, and the polyisocyanate (B) contains an aromatic polyisocyanate.

Effects of the Invention

[0008] The wet film-forming product of the present invention uses a polyurethane resin composition made from biomass raw materials and is an environmentally friendly material. Further, the polyurethane resin composition has excellent wet film-forming properties.

[0009] Therefore, the polyurethane resin composition of the present invention can be suitably used as a material for manufacturing synthetic leather, clothing, support pads, polishing pads, etc., and can be particularly suitably used as a material for synthetic leather.

Modes for Carrying Out the Invention

[0010] The wet film-forming product of the present invention is a wet film-forming product of a polyurethane resin composition, and the polyurethane resin composition contains a polyurethane resin (X) and an organic solvent (Y) using a specific polyol (A) and a specific polyisocyanate (B) as raw materials.

[0011] In order to obtain excellent wet film-forming properties, it is essential to use a polycarbonate polyol (A-1) using a biomass-derived decanediol as a raw material for the polyol (A).

[0012] As the content of the polycarbonate polyol (A-1) in the polyol (A), a range of 30 to 99.5% by mass is preferable, and a range of 50 to 90% by mass is more preferable, from the viewpoint of obtaining even more excellent wet film-forming properties.

[0013] As the polycarbonate polyol (A-1) using the biomass-derived decanediol as a raw material, for example, a reaction product of a glycol compound containing the biomass-derived decanediol and a carbonic ester and / or phosgene can be used, and specifically, those described in JP-A-2018-127758 and the like can be used.

[0014] As the decanediol, 1,10-decanediol is preferable from the viewpoint of obtaining even more excellent wet film-forming properties, oleic acid resistance, and low-temperature flexibility.

[0015] Examples of the glycol compound that can be used in addition to the decanediol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,5-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,8-nonanediol, 2-ethyl-2-butyl-1,3-propanediol, 1,12-dodecanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, trimethylolpropane, trimethylolethane, glycerin, ε-caprolactone, neopentyl glycol, and the like. These compounds may be used alone or in combination of two or more. Among these, butanediol is preferably used, and 1,4-butanediol is more preferably used, from the viewpoint of obtaining even more excellent wet film-forming properties, oleic acid resistance, and low-temperature flexibility.

[0016] When using the biomass-derived decanediol and the butanediol in combination, the total amount used is preferably 50 mol% or more, more preferably 70 mol% or more, and still more preferably 80 mol% or more in the glycol compound.

[0017] When using the biomass-derived decanediol (C10) and butanediol (C4) in combination, the molar ratio [(C4) / (C10)] is preferably in the range of 50 / 50 to 98 / 2, more preferably in the range of 75 / 25 to 95 / 5, from the viewpoint of obtaining even more excellent wet film-forming properties, oleic acid resistance, and low-temperature flexibility.

[0018] Examples of the carbonate ester include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate, etc. These compounds can be used alone or in combination of two or more.

[0019] The number average molecular weight of the polycarbonate diol (A-1) is preferably in the range of 500 to 100,000, more preferably in the range of 700 to 10,000, and still more preferably in the range of 1,500 to 4,000, from the viewpoint of obtaining even more excellent wet film-forming properties, oleic acid resistance, and low-temperature flexibility. The number average molecular weight of the polycarbonate diol (A-1) represents the value measured by the gel permeation chromatography (GPC) method.

[0020] Examples of the preferred polycarbonate polyol (A-1) include "Bene Biol NL-3010DB" manufactured by Mitsubishi Chemical Corporation, which can be obtained as a commercially available product.

[0021] As the polyol (A), other polyols can be used in combination in addition to the polycarbonate polyol (A-1). Examples of the other polyols include polyester polyols, polyether polyols, polybutadiene polyols, and polycarbonate polyols other than the polycarbonate polyol (A-1). These polyols may be used alone or in combination of two or more.

[0022] The number average molecular weight of the other polyol is preferably in the range of 200 to 100,000, more preferably in the range of 300 to 10,000, from the viewpoint of obtaining further excellent mechanical strength, wet film forming property, oleic acid resistance, and low temperature flexibility. The number average molecular weight of the other polyol indicates a value measured by gel permeation chromatography (GPC).

[0023] As the other polyol, it is preferable to use a polyether polyol, more preferably polyethylene glycol, from the viewpoint of excellent hydrophilicity and obtaining further excellent wet film forming property.

[0024] The number average molecular weight of the polyethylene glycol is preferably in the range of 250 to 1,500, more preferably in the range of 300 to 1,000, from the viewpoint of obtaining further excellent wet film forming property. The number average molecular weight of the polyethylene glycol indicates a value measured by gel permeation chromatography (GPC).

[0025] The mass ratio [(A-1) / (A-2)] of the polycarbonate polyol (A-1) to the polyether polyol (A-2) is preferably in the range of 50 / 50 to 99.5 / 0.5, more preferably in the range of 80 / 20 to 99 / 1, from the viewpoint of obtaining further excellent wet film forming property, abrasion resistance, oleic acid resistance, and low temperature flexibility.

[0026] If necessary, a chain extender (a) having a molecular weight in the range of 50 to 450 may be used in combination with the polyol (A).

[0027] Examples of the chain extender (a) include chain extenders having a hydroxyl group such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, trimethylolpropane, and glycerin; and chain extenders having an amino group such as ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, aminoethylethanolamine, hydrazine, diethylenetriamine, and triethylenetetramine. These chain extenders may be used alone or in combination of two or more. Among these, chain extenders having a hydroxyl group are preferred, and ethylene glycol and / or 1,4-butanediol are more preferred, in terms of being able to easily suppress the discoloration of the film over time, and further improving the wear resistance, oleic acid resistance, and low-temperature flexibility.

[0028] When using the chain extender (a), the amount used is preferably in the range of 1 to 50% by mass, more preferably in the range of 2 to 30% by mass, based on the total mass of the raw materials constituting the polyurethane resin (X), in terms of being able to further improve the wear resistance, oleic acid resistance, and low-temperature flexibility.

[0029] As the polyisocyanate (B), it is essential to use an aromatic polyisocyanate in order to obtain excellent wet film-forming properties. Examples of the aromatic polyisocyanate include 1,3- and 1,4-phenylene diisocyanate, 1-methyl-2,4-phenylene diisocyanate, 1-methyl-2,6-phenylene diisocyanate, 1-methyl-2,5-phenylene diisocyanate, 1-methyl-2,6-phenylene diisocyanate, 1-methyl-3,5-phenylene diisocyanate, 1-ethyl-2,4-phenylene diisocyanate, 1-isopropyl-2,4-phenylene diisocyanate, 1,3-dimethyl-2,4-phenylene diisocyanate, 1,3-dimethyl-4,6-phenylene diisocyanate, 1,4-dimethyl-2,5-phenylene diisocyanate, diethylbenzene diisocyanate, diisopropylbenzene diisocyanate, 1-methyl-3,5-diethylbenzene diisocyanate, 3-methyl-1,5-diethylbenzene-2,4-diisocyanate, 1,3,5-triethylbenzene-2,4-diisocyanate, naphthalene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, 1-methyl-naphthalene-1,5-diisocyanate, naphthalene-2,6-diisocyanate, naphthalene-2,7-diisocyanate, 1,1-dinaphthyl-2,2'-diisocyanate, biphenyl-2,4'-diisocyanate, biphenyl-4,4'-diisocyanate, 3-3'-dimethylbiphenyl-4,4'-diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, diphenylmethane-2,4-diisocyanate, etc. These compounds may be used alone or in combination of two or more. Among these, diphenylmethane diisocyanate is preferred in terms of obtaining even more excellent wet film-forming properties and mechanical strength.

[0030] The content of the aromatic polyisocyanate in the polyisocyanate (B) is preferably 50% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more.

[0031] For the polyisocyanate (B), other polyisocyanates may be used in combination as necessary. Examples of the other polyisocyanates include aliphatic or alicyclic polyisocyanates such as tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclopentylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, 1,3-di(isocyanatomethyl)cyclohexane, 1,4-di(isocyanatomethyl)cyclohexane, lysine diisocyanate, isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate, 2,2'-dicyclohexylmethane diisocyanate, 3,3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate, etc. These polyisocyanates may be used alone or in combination of two or more.

[0032] The amount of the polyisocyanate (B) used is preferably in the range of 10 to 60% by mass, more preferably in the range of 15 to 45% by mass, based on the total mass of the raw materials constituting the polyurethane resin (X), from the viewpoint of obtaining even more excellent wet film-forming properties, mechanical strength, and reactivity.

[0033] Examples of the method for producing the polyurethane resin (X) include a method in which the polyol (A) and the polyisocyanate (B) are charged and reacted all at once. The reaction is preferably carried out at a temperature of 30 to 100°C for 3 to 10 hours. Further, the reaction may be carried out in an organic solvent (Y) described later.

[0034] The number average molecular weight of the polyurethane resin (X) obtained by the above method is preferably in the range of 5,000 to 1,000,000, more preferably in the range of 10,000 to 500,000, from the viewpoint of further improving abrasion resistance, oleic acid resistance, low-temperature flexibility, mechanical strength and flexibility of the film. The number average molecular weight of the polyurethane resin (X) represents the value measured by the gel permeation chromatography (GPC) method.

[0035] The content of the polyurethane resin (X) is preferably in the range of 10 to 90% by mass, more preferably in the range of 15 to 80% by mass in the polyurethane resin composition.

[0036] Examples of the organic solvent (B) include ketone solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, methyl ethyl ketone, methyl-n-propyl ketone, acetone, and methyl isobutyl ketone; ester solvents such as methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, isopropyl acetate, isobutyl acetate, isobutyl acetate, and sec-butyl acetate; and alcohol solvents such as methanol, ethanol, isopropyl alcohol, and butanol. These organic solvents can be used alone or in combination of two or more.

[0037] The content of the organic solvent (B) is preferably in the range of 20 to 90% by mass in the polyurethane resin composition from the viewpoints of workability and viscosity.

[0038] The polyurethane resin composition contains the polyurethane resin (X) and the organic solvent (Y) as essential components, and may contain other components as required.

[0039] Examples of the other components include pigments, flame retardants, plasticizers, softeners, stabilizers, waxes, defoamers, dispersants, penetrants, surfactants, fillers, antifungal agents, antibacterial agents, ultraviolet absorbers, antioxidants, weather stabilizers, fluorescent brighteners, anti-aging agents, thickeners, etc. These components may be used alone or in combination of two or more.

[0040] Next, a method for producing a wet film (porous body) from the polyurethane resin composition by a wet film-forming method will be described.

[0041] The wet film-forming method is a method for producing a porous body by applying or impregnating the polyurethane resin composition on the surface of a substrate and then bringing water, water vapor, etc. into contact with the applied surface or impregnated surface to solidify the polyurethane resin (A).

[0042] Examples of the substrate on which the polyurethane resin composition is applied include substrates made of non-woven fabric, woven fabric, and knitted fabric; resin films, etc. Examples of what constitutes the substrate include chemical fibers such as polyester fiber, nylon fiber, acrylic fiber, polyurethane fiber, acetate fiber, rayon fiber, and polylactic acid fiber; cotton, hemp, silk, wool, and blended fibers thereof, etc. can be used.

[0043] The surface of the substrate may be subjected to treatments such as antistatic processing, mold release processing, water repellent processing, water absorption processing, antibacterial and deodorant processing, bacteriostatic processing, ultraviolet blocking processing, etc. as required.

[0044] Examples of the method for applying or impregnating the polyurethane resin composition on the substrate surface include the gravure coater method, knife coater method, pipe coater method, comma coater method. In that case, in order to adjust the viscosity of the polyurethane resin composition and improve the coating workability, the amount of the organic solvent (B) used may be adjusted as required.

[0045] The film thickness of the coating film made of the polyurethane resin composition applied or impregnated by the above method is preferably in the range of 0.5 to 5 mm, more preferably in the range of 0.5 to 3 mm.

[0046] As a method of bringing water or water vapor into contact with the coated surface formed by applying or impregnating the polyurethane resin composition, for example, a method of immersing the substrate provided with the coating layer or impregnation layer made of the polyurethane resin composition in a water bath; a method of spraying water using a spray or the like on the coated surface can be mentioned. The immersion is preferably carried out in a water bath at 5 to 60 °C for about 2 to 20 minutes.

[0047] The wet film-formed product obtained by the above method is preferably washed on its surface with normal-temperature water or warm water to extract and remove the organic solvent (B), and then dried. The washing is preferably carried out with water at 5 to 60 °C for about 20 to 120 minutes, and the water used for washing is preferably replaced one or more times or continuously replaced with running water. The drying is preferably carried out using a dryer adjusted to 80 to 120 °C for about 10 to 60 minutes.

Example

[0048] Hereinafter, the present invention will be described in more detail using examples.

[0049] [Example 1] [Preparation of Polyurethane Resin Composition (1)] In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 280 parts by mass of a polycarbonate diol (molar ratio [(C4) / (C10)] = 90 / 10, number average molecular weight; 2,000, hereinafter abbreviated as "bio-PC(1)") made from 1,4-butanediol and biomass-derived 1,10-decanediol, 20 parts by mass of polyethylene glycol (number average molecular weight; 600, hereinafter abbreviated as "PEG(1)"), 14 parts by mass of ethylene glycol, and 930 parts by mass of N,N-dimethylformamide (hereinafter abbreviated as "DMF") were added and stirred well. After stirring, 100 parts by mass of diphenylmethane diisocyanate (hereinafter abbreviated as "MDI") was added and reacted at 80 °C for 3 hours to obtain a polyurethane resin composition with a solid content of 30% by mass (bio ratio; 17%).

[0050] <Preparation of wet film-forming product> The obtained polyurethane resin composition was diluted with 60 parts by mass of DMF, and the resulting formulation was coated on a polyethylene terephthalate film with a clearance of 1 mm. Then, it was immersed in water at 25 °C for 10 minutes, washed with warm water at 40 °C for 1 hour, and dried in a dryer at 100 °C for 30 minutes to obtain a wet film-forming product.

[0051] [Example 2] A polyurethane resin composition was obtained in the same manner as in Example 1 except that the amount of bio-PC(1) used was changed from 280 parts by mass to 240 parts by mass and the amount of PEG(1) used was changed from 20 parts by mass to 60 parts by mass, and a wet film-forming product was obtained.

[0052] [Example 3] A polyurethane resin composition was obtained in the same manner as in Example 1 except that the type of bio-PC(1) was changed to a polycarbonate diol (molar ratio [(C4) / (C10)] = 80 / 20, number average molecular weight; 2,000, hereinafter abbreviated as "bio-PC(2)") made from 1,4-butanediol and biomass-derived 1,10-decanediol, and a wet film-forming product was obtained.

[0053] [Example 4] A polyurethane resin composition was obtained in the same manner as in Example 1 except that the amount of the bio-PC (2) was changed from 280 parts by mass to 240 parts by mass and the amount of the PEG (1) was changed from 20 parts by mass to 60 parts by mass, and a wet film was obtained.

[0054] [Example 5] A polyurethane resin composition was obtained in the same manner as in Example 1 except that the type of the PEG (1) was changed to polyethylene glycol (number average molecular weight; 400, hereinafter referred to as "PEG (2)"), and a wet film was obtained.

[0055] [Comparative Example 1] A polyurethane resin composition was obtained in the same manner as in Example 1 except that the type of the MDI was changed to hexamethylene diisocyanate (hereinafter abbreviated as "HDI"), and an attempt was made to produce a wet film.

[0056] [Measurement method of number average molecular weight] The number average molecular weights of the polyols and the like used in the examples and comparative examples are the values measured under the following conditions by the gel permeation chromatography (GPC) method.

[0057] Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were connected in series and used. "TSKgel G5000" (7.8 mm I.D. × 30 cm) × 1 piece "TSKgel G4000" (7.8 mm I.D. × 30 cm) × 1 piece "TSKgel G3000" (7.8 mm I.D. × 30 cm) × 1 piece "TSKgel G2000" (7.8 mm I.D. × 30 cm) × 1 piece Detector: RI (differential refractometer) Column temperature: 40 °C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4% by mass) Standard sample: A calibration curve was created using the following standard polystyrenes.

[0058] (Standard polystyrene) "TSKgel Standard Polystyrene A-500" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene A-1000" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene A-2500" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene A-5000" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-1" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-2" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-4" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-10" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-20" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-40" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-80" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-128" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-288" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation

[0059] [Evaluation method for wet film-forming property] The wet films obtained in the examples and comparative examples were observed using a scanning electron microscope "SU3500" (magnification: 500 times) manufactured by Hitachi High-Technologies Corporation to confirm whether a porous body was formed. Those in which a porous body could be confirmed were evaluated as "〇", and those in which it could not be confirmed were evaluated as "×". "〇": Uniformly shaped pores were confirmed. "△": Non-uniform pores were confirmed. "×": Pores could not be confirmed.

[0060]

Table 1

[0061]

Table 2

[0062] Examples 1 to 5, which are the wet film-forming materials of the present invention, were found to be excellent in wet film-forming properties.

[0063] On the other hand, Comparative Example 1 is a mode in which an aliphatic polyisocyanate is used instead of an aromatic polyisocyanate, but the wet film-forming property was poor.

Claims

【Claim 1】 A wet film formed from a polyurethane resin composition containing a polyurethane resin (X) and an organic solvent (Y), where the polyurethane resin (X) is made from a polyol (A) and a polyisocyanate (B), the polyol (A) contains a polycarbonate polyol (A-1) made from butanediol and a biomass-derived decanediol, and a polyether polyol (A-2) containing polyethylene glycol, the mass ratio [(A-1) / (A-2)] of the polycarbonate polyol (A-1) to the polyether polyol (A-2) is in the range of 80 / 20 to 99 / 1, the number average molecular weight of the polyethylene glycol is in the range of 250 to 400, the molar ratio [butanediol (C4) / decanediol (C10)] of the butanediol to the decanediol is in the range of 75 / 25 to 95 / 5, and the polyisocyanate (B) contains an aromatic polyisocyanate. A wet film characterized by this.

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